Production of supported olefin polymerization catalysts

ABSTRACT

The invention provides a process for producing an olefin polymerisation catalyst, comprising suspending a porous particulate support material in a liquid/liquid two phase system which comprises a solution of one or more catalyst components and an inert solvent immiscible therewith, to impregnate said solution into the pores of said support material, and optionally solidifying said impregnated solution present in the pores of said support particles.

This invention relates to a process for the production of supportedcatalysts for olefin polymerisation, and their use in polymerisingolefins.

BACKGROUND ART

Catalyst systems which are solutions of one or more catalyst components(e.g. a transition metal compound and optionally a cocatalyst) are knownin the filed as homogeneous catalyst systems. Homogeneous systems areused as liquids in the polymerisation process. Such systems have ingeneral a satisfactory catalytic activity, but their problem has beenthat the polymer thus produced has a poor morphology (e.g. the endpolymer is in a form of a fluff having a low bulk density). As aconsequence, operation of slurry and gas phase reactors using ahomogeneous catalyst system cause problems in practice as i.a. foulingof the reactor can occur.

To overcome the problems of the homogeneous systems in a non-solutionprocess the catalyst components have been supported, e.g. their solutionimpregnated, on porous organic or inorganic support material, e.g.silica. These supported systems, known as heterogeneous catalystsystems, can additionally be prepolymerised in order to furtherimmobilise and stabilise the catalyst components.

However, also supported and optionally prepolymerised systems haveproblems. It is difficult to get an even distribution of the catalystcomponents in the porous carrier material; and leaching of the catalystcomponents from the support can occur. Such drawbacks lead to anunsatisfactory polymerisation behaviour of the catalyst, and as a resultthe morphology of the polymer product thus obtained is also poor.Furthermore, the uneven distribution of the catalyst components in thesupport material can have an adverse influence on the fragmentationbehaviour of the support material during the polymerisation step.

The support can also have an adverse effect on the activity of thecatalyst, on its polymerisation behaviour and on the properties of theend polymer.

Accordingly, prior art proposes a variety of different means forachieving an even distribution of the catalyst component(s) into thepores of a support material, and in particular various impregnationmethods have been suggested: The support material can be slurried in thesolution of the catalyst components, or said solution is added to thesilica in a volume which is equal or less than the total pore volume ofthe used silica (see e.g. WO 95 12622 of Borealis). WO 97 17136 of Mobiloil discloses a method wherein Mg-treated silica is slurried to analiphatic solvent, e.g. isopentane and a toluene solution of ametallocene and aluminoxane is added to the slurry. The catalystcomponents are allowed to impregnate in the formed mixture and finallythe solvents of the mixture are removed by evaporation. EP 295 312 ofMitsui discloses a method wherein aluminoxane in a first solvent isprecipitated by adding a second solvent wherein aluminoxane isinsoluble, in the presence of a carrier to deposit the precipitatedaluminoxane on the carrier.

WO 97 02297 of Exxon describes a variation of a conventional slurryprepolymerisation method wherein the amount of the solvent used for thesupported catalyst particles during the prepolymerisation step isreduced to a volume equal or less than the total pore volume of thesupported catalyst. According to said document said prepolymerisationconditions has to be adjusted to avoid any clumping problems due to thecondensation of the solvent (which may lead to the migration of thecatalyst components already encountered with the prior art slurryprepolymerisation method).

Due to the complexity of the catalyst systems, the need still exists todevelop further catalyst systems and preparation methods thereof whichovercome the problems of the prior art practice.

SUMMARY OF THE INVENTION

The present invention provides a further method for preparing asupported catalyst for polyolefin polymerisation.

Another object of the invention is to provide a solid catalyst withadvantageous properties.

A further object is to provide a polymerisation process using thecatalyst prepared according to the method of the invention, as well as asupported catalyst obtainable by the method of the invention.

DESCRIPTION OF THE INVENTION

The invention is based on the finding that an even distribution of thecatalyst component(s) in a porous particulate support material can beachieved by impregnating a solution of one or more catalyst componentsinto a porous support in a mixed liquid/liquid at least two phase systemwhich comprises said solution of the catalyst component(s) and a solventimmiscible therewith.

Moreover, the inventors have also found that it is possible to furtherimmobilise a solution of the catalyst component(s) impregnated into thepores of a porous particulate support material by suspending saidimpregnated support, containing said solution within the pores thereof,in a solvent immiscible with said solution and immobilising the catalystcomponent(s) of said solution within the pores of the dispersed support.

The features of the invention are defined in the claims.

Accordingly, the invention provides a process for producing a supportedolefin polymerisation catalyst, comprising one or more active componentswhich include a compound of a transition metal of Group 3 to 10 of thePeriodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 1989),comprising suspending particles of a porous support material in amixture of a solution of said component or components with a solventimmiscible with said solution, and optionally recovering from theagitated mixture support particles impregnated by said solution.

As stated above the liquid/liquid at least two phase system of theinvention can also be used for further immobilising a supported catalystby dispersing (suspending) the porous support particles, which contain asolution of catalyst component(s) within the pores thereof, in a solventimmiscible with said solution and then solidifying the catalystcomponent(s) containing phase present in the pores of the dispersedsupport. The filling of the pores of the support material with saidsolution before carrying out the immobilisation step of the inventioncan be effected using the two phase impregnation step of the inventiondescribed above, whereby said solidification step can be carried outdirectly after the impregnation step, in the same “two phase” system, asa “one-pot” procedure. Alternatively, other suitable pore fillingmethods can also be used, e.g. those known from the prior art,whereafter, without removing said solution from the pores, the obtainedimpregnated particles can be suspended to a solvent immiscible with saidsolution and subjected to the solidification step of the invention.

Preferably, the support is impregnated according to the two phase systemof the invention followed by, without any recovery of the impregnatedparticles from the immiscible solvent, the immobilisation step of theinvention. I.e. said solution of the mixed liquid/liquid two phasesystem which contains the catalyst component(s) is sorbed into the poresof the support particles and then the sorbed phase is solidified withinthe pores of said particles surrounded by the immiscible solvent phase.Finally the particles of the immobilised supported catalyst arerecovered, if desired.

Accordingly, in the method of the present invention, the solution of thecatalyst component(s) forms the discontinuous phase which impregnates tothe pores of the support and the solvent immiscible therewith forms thecontinuous phase surrounding the impregnated support particles.

The terms “immobilisation” and “solidification” are used hereininterchangeably for the same purpose, i.e. for further “fixing” thecatalyst component(s) to the support material and to achievefree-flowing solid catalyst particles. Said step can thus be effected invarious ways: (i) by effecting a prepolymerisation reaction within saidsolution of catalyst component(s) impregnated to the pores of thesupport, (ii) by cross-linking, e.g. fully or partially cross-linking acatalyst component within the said impregnated solution by adding across-linking agent, (iii) by effecting a chemical reaction withinimpregnated solution whereby the reaction product precipitates(“solidifies”), and/or (iv) by causing an external stimulus to theemulsion system such as a temperature change to cause thesolidification. Thus in said step the catalyst component(s) remain“fixed” within the pores of the support. It is also possible that one ormore of the catalyst components may take part in thesolidification/immobilisation reaction.

The supported catalyst obtained is in the form of compositionallyuniform particles having a predetermined size range.

In a further embodiment of the invention said mixture is in a form of anemulsion, wherein the solution of the catalyst components constitutesthe dispersed phase and the solvent the continuous phase.

Accordingly, the carrier particles may be suspended in said immisciblesolvent before or after mixing of said solution therewith: alternativelythey may be suspended in the solution and this added to the immisciblesolvent. In a further effective impregnation procedure comprises:forming first a one phase liquid system of the solvent and the catalystcomponent(s) containing solution (e.g. by adjusting the temperature),then adding of the support particles and, finally, breaking of the onephase system to at least two liquid phases as by changing thetemperature, whereby the dispersed phase impregnates to the pores of thecarrier.

The invention is also industrially advantageous, since it enables thepreparation of immobilised solid catalyst particles to be carried out asa one-pot procedure.

Dispersed Phase

The principles for preparing two phase systems are known in the chemicalfield. Thus, in order to form the two phase liquid system, the solutionof the catalyst component(s) and the solvent used as the continuousliquid phase have to be essentially immiscible at least during themixing step and, e.g. in case the carrier material is added after thecatalyst solution and the immiscible solvent are combined, during theimpregnation step of said solution into the pores of the support. Thiscan be achieved in a known manner e.g. by choosing said two liquidsand/or the temperature of the dispersing and impregnation and/orimmobilisation step accordingly.

It has been found that when the two phase mixture or an emulsion of theinvention is formed, the solution containing the catalyst component(s)will advantageously displace from the pores of the carrier any of theimmiscible liquid which might have been sorbed. Any excess solution maybe permitted to separate from the immiscible phase, and may easily beremoved, as by decanting.

The impregnated and/or immobilised supported catalyst of the inventioncan be separated from the continuous phase, e.g. by filtration, andoptionally washed with a suitable solvent and/or dried in a conventionalmanner.

A solvent may be employed to form the solution of the catalystcomponent(s). Said solvent is chosen so that it dissolves said catalystcomponent(s). The solvent can be preferably an organic solvent such asused in the field comprising an optionally substituted hydrocarbon, suchas a linear or branched aliphatic, alicyclic or aromatic hydrocarbon,preferably a linear or cyclic alkane or alkene, an aromatic hydrocarbonand/or a halogen containing hydrocarbon. Examples of aromatichydrocarbons are toluene, benzene, ethylbenzene, propylbenzene,butylbenzene and xylene. Toluene is a preferred solvent. The solutionmay comprise one or more solvents.

In another embodiment, it consists partly or completely of a liquidmonomer, preferably an olefin monomer, designed to be polymerised in a“prepolymerisation” immobilisation step.

Continuous Phase

The solvent used to form the continuous liquid phase is chosen from asingle solvent or a mixture of solvents and immiscible with the solutionof the catalyst component(s) at least at the conditions (e.g.temperatures) used during the mixing/dispersing step and impregnationstep, if the impregnation is effected after the mixing step of said twophase forming liquids.

Preferably said solvent is inert in relation to said compounds. The term“inert in relation to said compounds” means herein that the continuousphase is chemically inert, i.e. undergoes no chemical reaction with anycatalyst forming component or catalyst precursor forming component.Thus, the catalyst compounds which are fixed to the pores of the carrieroriginate from the catalyst solution to be impregnated into the pores.

It is preferred that the catalyst component(s) used for forming thesupported catalyst, as defined under “catalyst compounds” below, willnot be soluble in the solvent of the continuous liquid phase.Preferably, said catalyst component(s) are essentially insoluble in saidcontinuous phase forming solvent.

The term “liquid/liquid at least two phase system” used herein coversboth bi- and multiphasic systems.

In cases where the solvent is removed from the catalyst solution (e.g.due to a temperature change) to cause the solidification of the activeingredients, said solidifying ingredients remain essentially in thepores of the carrier.

In a preferred embodiment of the invention said solvent forming thecontinuous phase is an inert solvent and includes halogenated organicsolvents, particularly fluorinated organic solvents, preferably semi,highly or perfluorinated organic solvents and functionalised derivativesthereof, which means that said solvents may contain other functionalgroups and/or further halogens such as chlorine.

Examples of the above-mentioned solvents are semi, highly orperfluorinated (a) hydrocarbons, such as alkanes, alkenes andcycloalkanes, (b) ethers, e.g. perfluorinated ethers and (c) amines,particularly tertiary amines, and functionalised derivatives thereof.Preferred are perfluorohydrocarbons of e.g. C3-C30, such as C4-C10.Specific examples of suitable perfluoroalkanes and -cycloalkanes includeperfluorohexane, -heptane, -octane and -(methylcyclohexane). Semifluorinated hydrocarbons relates particularly to semifluorinatedn-alkanes, such as perfluoroalkyl-alkane.

“Semi fluorinated” hydrocarbons also include such hydrocarbons whereinblocks of —C—F and —C—H alternate. “Highly fluorinated” means that themajority of the —C—H units are replaced with —C—F units.“Perfluorinated” means that all —C—H units are replaced with —C—F units.In this respect, it is referred to the articles of A. Enders and G. Maasin “Chemie in unserer Zeit”, 34. Jahrg. 2000, Nr.6, and of Pierandrea LoNostro in “Advances in Colloid and Interface Science, 56 (1995) 245-287,Elsevier Science.

The fluorinated solvents are particularly preferred as they are apolar,hydrophobic and have very limited miscibility with common organicsolvents in certain temperature ranges.

Furthermore, these fluorinated solvents are chemically very inert andare very poor solvents for polar compounds such as catalytically activecompounds and precursors or reaction products thereof. This finding ofthe inventors is very important in the formation of catalyst particles,because the reactive compounds can be kept within the catalyst solutionin the pores of the support material so that no relevant reactions inthe continuous phase which would worsen e.g. the morphology of thesolidified catalyst particles can be observed.

Support Material

The support (carrier) material can be any porous particulate materialusable as a support, e.g. any support material conventionally used inthe field, such as an inorganic or organic material, e.g. an organic orinorganic polymeric material. Preferably, the support is a metal ormetalloid oxide such as silica or alumina, or a mixture thereof.Particularly, silica can be used.

The support material may be treated before subjecting to the two phasesystem. The treatment can be used for modifying the properties of thesupport, e.g. the acidity, for removing any water and/or e.g. in case ofsilica for reducing the hydroxy functionalities on the support.Alternatively, the support material can be treated to introduce anydesired functionalities on the support material. A further possibilityis to pretreat the support material with a cocatalyst(s) beforesubjecting to the method of the invention. The mentioned treatments arewithin the knowledge of a person skilled in the art and include e.g. aheat (calcination) and a chemical treatment.

The particle size and porosity of support material can be chosendepending e.g. on the desired polymerisation behaviour of the catalyst.E.g. an average particle size range may vary between 1 to 500 μm, e.g. 5to 500 μm, advantageously 5 to 200 μm, e.g. 10 to 100 μm, such as 20 to50 μm, and a pore volume between 0.1 to 4 ml/g. Commercially availablesupport materials with varying composition, particle size, pore size,total pore volume, surface area etc. (e.g. Davison 948 available fromDavision Chemical Company, Baltimore, Md., US, or Sylopol 55, availablefrom Grace) are usable in this invention.

The quantity of carrier employed varies according to its porosity, andaccording to the volume of solution employed.

Dispersing Step

The dispersion/suspension can be formed by any means known in the art:by mixing, such as by stirring said solution (vigorously) to saidsolvent forming the continuous phase or by means of mixing mills, or bymeans of ultra sonic wave. The mixing may be effected at lower orelevated temperatures, e.g. between 0 and 100° C., depending i.a. on theused solvents, and is chosen accordingly.

A further possibility is, as stated above, to use a so called “onephase” change method for preparing the two phase system by first forminga homogeneous system which is then changed by changing the temperatureof the system to a biphasic system. Preferably, the support material isadded to the one phase system before the change to the biphasic system.If needed, part of the catalyst forming compounds may be added after thebiphasic system is formed.

The formation of a two phase system via said “one phase” change may beone preferable method, especially when e.g. fluorinated solvents areused as the continuous phase, since the miscibility of the fluorinatedsolvents, in particular perfluorinated solvents, with common organicsolvents (e.g. alkane, such as pentane, hexane, chloroform, toluene) isdependent on the temperature so that a one phase system (homogeneousphase) of the fluorous solvent and a common organic solvent can beformed above a certain critical temperature.

The impregnation of the catalyst solution may be effected before orafter the dispersion of the support material to said immiscible solventas the continuous phase.

The dispersion step and the solidification step are preferably effected,as for example, under appropriate stirring.

The ratio of the first (e.g. fluorous solvent) and second solvent(common organic solvent as defined above for the “Continuous Phase”) ischosen so that the first solution forms the discontinuous phase in theat least two phase system. The volume ratio of solution of the catalystcomponent(s) to the immiscible liquid forming the continuous phase isnot narrowly critical. Suitably, said solution is used in a volume whichis less or equal to the total pore volume of the support material, andpreferably corresponds essentially to the total pore volume of thesupport material. Any excess of said solution remained after theimpregnation step may be allowed to separate from the immisciblecontinuous phase and/or support material and can be removed before theoptional immobilisation of step of the supported particles.Alternatively, the entire catalyst solution can be brought to theimmiscible solvent (continuous phase) within the pores of the support.

In a preferred operation the process is so conducted that the volume ofsolution employed is entirely sorbed by the carrier particles, thusrendering unnecessary any post-impregnation separation of excesssolution or carrier.

The continuous phase is preferably used in an amount which enables thesuspending (and surrounding) the particles.

In the preparation process of the invention the solution to beimpregnated to the pores of the carrier may already contain all thecompounds (to be added) before the impregnation step thereof.Alternatively, e.g. depending on the reactivity of the compounds, atleast two separate catalyst solutions for each or part of the catalystforming compounds may be prepared, which are then impregnatedsuccessively into the pores.

Additional agents and/or components can be added to the system in anystage of the impregnation and/or solidification step, if needed.

Catalyst Compounds

The term “catalyst component” as used herein includes, in addition tosaid transition metal compound, also any additional cocatalyst(s). (e.g.additional transition metal compounds and/or activators and/or poisonscavengers) and/or any reaction product(s) of a transition compound(s)and a cocatalyst(s). Thus the catalyst may be formed in situ from thecatalyst components in said solution in a manner known in the art.

It should also be understood that the catalyst prepared according to theinvention may be used as such in the polymerisation process or mayrepresent a “catalyst precursor” which is further activated or treatedto form the active catalyst system. Furthermore, said catalyst of theinvention may be part of a further catalyst system. These alternativesare within the knowledge of a skilled person.

The term “transition metal compound” can be any transition metalcompound which exhibits the catalytic activity alone or together with acocatalyst/activator. The transition metal compounds are well known inthe art and cover e.g. compounds of metals from Group 3 to 10, e.g. 3 to7, such as Group 4 to 6, (IUPAC), as well as lanthanides or actinides.

A preferable subgroup of the transition metal compounds areorganometallic compounds of a transition metal which, as used herein,includes any metallocene or non-metallocene compound of a transitionmetal which bears at least one organic (co-ordination) ligand andexhibits the catalytic activity alone or together with a cocatalyst.

Accordingly, said organotransition metal compound may have the followingformula I:(L)_(m)R_(n)MX_(q)  (I)wherein M is a transition metal as defined above and each X isindependently a monovalent anionic ligand, such as a σ-ligand, each L isindependently an organic ligand which coordinates to M, R is a bridginggroup linking two ligands L, m is 1, 2 or 3, n is 0, 1 or 2, preferably0 or 1, q is 1, 2 or 3, and m+q is equal to the valency of the metal.

In a more preferred definition, each L is independently (a) asubstituted or unsubstituted cyclopentadiene or a mono-, bi- ormultifused derivative of a cyclopentadiene which optionally bear furthersubstituents and/or one or more hetero ring atoms from a Group 13 to 16of the Periodic Table (IUPAC); or (b) an acyclic, η¹- to η⁴- orη⁶-ligand composed of atoms from Groups 13 to 16 of the Periodic Table,and in which the open chain ligand may be fused with one or two,preferably two, aromatic or non-aromatic rings and/or bear furthersubstituents; or (c) a cyclic σ-, η¹- to η⁴- or η⁶-mono-, bi- ormultidentate ligand composed of unsubstituted or substituted mono-, bi-or multicyclic ring systems selected from aromatic or non-aromatic orpartially saturated ring systems, and containing carbon ring atoms andoptionally one or more heteroatoms selected from Groups 15 and 16 of thePeriodic Table.

By “σ-ligand” is meant a group bonded to the metal at one or more placesvia a sigma bond.

According to a preferred embodiment said organotransition metal compoundI is a group of compounds known as metallocenes. Said metallocenes bearat least one organic ligand, generally 1, 2 or 3, e.g. 1 or 2, which isq-bonded to the metal, e.g. a η²⁻⁶-ligand, such as a η⁵-ligand.Preferably, a metallocene is a Group 4 to 6 transition metal, suitablytitanocene, zirconocene or hafnocene, which contains at least oneη⁵-ligand, which is e.g. an optionally substituted cyclopentadienyl, anoptionally substituted indenyl, an optionally substitutedtetrahydroindenyl or an optionally substituted fluorenyl.

The metallocene compound may have a formula II:(Cp)_(m)R_(n)MX_(q)  (II)wherein:

-   -   each Cp independently is an unsubstituted or substituted and/or        fused homo- or heterocyclopentadienyl ligand, e.g. substituted        or unsubstituted cyclopentadienyl, substituted or unsubstituted        indenyl or substituted or unsubstituted fluorenyl ligand; the        optional one or more substituent(s) being selected preferably        from halogen, hydrocarbyl (e.g. C1-C20-alkyl, C2-C20-alkenyl,        C2-C20-alkynyl, C3-C12-cycloalkyl, C6-C20-aryl or        C7-C20-arylalkyl), C3-C12-cycloalkyl which contains 1, 2, 3 or 4        heteroatom(s) in the ring moiety, C6-C20-heteroaryl,        C1-C20-haloalkyl, —SiR″₃, —OSiR″₃, —SR″, —PR″₂ or —NR″₂, each R″        is independently a hydrogen or hydrocarbyl, e.g. C1-C20-alkyl,        C2-C20-alkenyl, C2-C20-alkynyl, C3-C12-cycloalkyl or        C6-C20-aryl; or e.g. in case of —NR″₂, the two substituents R″        can form a ring, e.g. five- or six-membered ring, together with        the nitrogen atom wherein they are attached to;    -   R is a bridge of 1-7 atoms, e.g. a bridge of 1-4 C-atoms and 0-4        heteroatoms, wherein the heteroatom(s) can be e.g. Si, Ge and/or        O atom(s), whereby each of the bridge atoms may bear        independently substituents, such as C1-C20-alkyl,        tri(C1-C20-alkyl)silyl, tri(C1-C20-alkyl)siloxy or C6-C20-aryl        substituents); or a bridge of 1-3, e.g. one or two, hetero        atoms, such as silicon, germanium and/or oxygen atom(s), e.g.        —SiR¹ ₂—, wherein each R¹ is independently C1-C20-alkyl,        C6-C20-aryl or tri(C1-C20-alkyl)silyl-residue, such as        trimethylsilyl-;    -   M is a transition metal of Group 4 to 6, such as Group 4, e.g.        Ti, Zr or Hf,    -   each X is independently a sigma-ligand, such as H, halogen,        C1-C20-alkyl, C1-C20-alkoxy, C2-C20-alkenyl, C2-C20-alkynyl,        C3-C12-cycloalkyl, C6-C20-aryl, C6-C20-aryloxy,        C7-C20-arylalkyl, C7-C20-arylalkenyl, —SR″, —PR″₃, —SiR″₃,        —OSiR″₃ or —NR″₂; each R″ is independently hydrogen or        hydrocarbyl, e.g. C1-C20-alkyl, C2-C20-alkenyl, C2-C20-alkynyl,        C3-C12-cycloalkyl or C6-C20-aryl; or e.g. in case of —NR″₂, the        two substituents R″ can form a ring, e.g. five- or six-membered        ring, together with the nitrogen atom wherein they are attached        to;    -   and each of the above mentioned ring moiety alone or as a part        of a moiety as the substituent for Cp, X, R” or R¹ can further        be substituted e.g. with C₁-C₂₀-alkyl which may contain Si        and/or O atoms;

-   n is 0, 1 or 2, preferably 0 or 1,

-   m is 1, 2 or 3, e.g. 1 or 2,

-   q is 1, 2 or 3, e.g. 2 or 3,    wherein m+q is equal to the valency of M.

Said metallocenes II and their preparation are well known in the art.

Cp is preferably cyclopentadienyl, indenyl, tetrahydroindenyl orfluorenyl, optionally substituted as defined above and may further beara fused ring of 3 to 7 atoms, e.g. 4, 5 or 6, which ring may be aromaticor partially saturated.

In a suitable subgroup of the compounds of formula II each Cpindependently bears one or more substituents selected from C1-C20-alkyl,C6-C20-aryl, C7-C20-arylalkyl (wherein the aryl ring alone or as a partof a further moiety may further be substituted as indicated above),—OSiR″₃, wherein R″ is as indicated above, preferably C1-C20 alkyl; X isas H, halogen, C1-C20-alkyl, C1-C20-alkoxy, C6-C20-aryl,C7-C20-arylalkenyl or —NR″₂ as defined above, e.g. —N(C1-C20alkyl)₂; Ris a methylene, ethylene or a silyl bridge, whereby the silyl can besubstituted as defined above, e.g. a dimethylsilyl=,methylphenylsilyl=or trimethylsilylmethylsilyl=bridge; n is 0 or 1; m is2 and q is two.

Preferably, R″ is other than hydrogen.

A specific subgroup includes the well known metallocenes of Zr, Hf andTi with one or two, e.g. two, η⁵-ligands which may be bridged orunbridged cyclopentadienyl ligands optionally substituted with eg.siloxy, alkyl and/or aryl as defined above, or with two unbridged orbridged indenyl ligands optionally substituted in any of the ringmoieties with eg. siloxy, alkyl and/or aryl as defined above, e.g. at2-, 3-, 4- and/or 7-positions. As specific examples e.g.bis(alkylcyclopentadienyl)Zr (or Ti or Hf) dihalogenides can bementioned, such as bis(n-butylcyclopentadienyl)ZrCl2 andbis(n-butylcyclopentadienyl)HfCl2, see e.g. EP-A-129 368. Examples ofcompounds wherein the metal atom bears a —NR″₂ ligand are disclosed i.a.in WO-A-9856831 and WO-A-0034341. The contents of the above documentsare incorporated herein by reference. Further metallocenes are describede.g. in EP-A-260 130. As further examples of usable metallocenes mayalso be found e.g. from WO-A-9728170, WO-A-9846616, WO-A-9849208,WO-A-9912981, WO-A-9919335, WO-A-9856831, WO-A-0034341, EP-A-423 101 andEP-A-537 130 as well as V. C. Gibson et al., in Angew. Chem. Int. Ed.,engl., vol 38, 1999, pp 428-447, the disclosures of which areincorporated herein by reference.

Alternatively, in a further subgroup of the metallocene compounds, themetal bears a Cp group as defined above and additionally a η¹ or η²ligand, wherein said ligands may or may not be bridged to each other.This subgroup includes so called “scorpionate compounds” (withconstrained geometry) in which the metal is complexed by a η⁵ ligandbridged to a η¹ or η² ligand, preferably η¹ (for example a σ-bonded)ligand, e.g. a metal complex of a Cp group as defined above, e.g. acyclopentadienyl group, which bears, via a bridge member, an acyclic orcyclic group containing at least one heteroatom, e.g. —NR₁₂ as definedabove. Such compounds are described e.g. in WO-A-9613529, the contentsof which are incorporated herein by reference.

Any alkyl, alkenyl or alkynyl residue referred above alone or as a partof a moiety may be linear or branched, and contain preferably of up to9, e.g. of up to 6, carbon atoms. Aryl is preferably phenyl ornaphthalene. Halogen means F, Cl, Br or I, preferably Cl.

Another subgroup of the organotransition metal compounds of formula Iusable in the present invention is known as non-metallocenes wherein thetransition metal (preferably a Group 4 to 6 transition metal, suitablyTi, Zr or Hf) has a co-ordination ligand other than cyclopentadienylligand.

The term “non-metallocene” herein means compounds, which bear nocyclopentadienyl ligands or fused derivatives thereof, but one or morenon-cyclopentadienyl η- or σ-, mono-, bi- or multidentate ligand. Suchligands can be chosen e.g. from (a) acyclic, η¹- to η⁴ or η⁶-ligandscomposed of atoms from Groups 13 to 16 of the Periodic Table (IUPAC),e.g. an acyclic pentadienyl ligand wherein the chain consists of carbonatoms and optionally one or more heteroatoms from Groups 13 to 16(IUPAC), and in which the open chain ligand may be fused with one ortwo, preferably two, aromatic or non-aromatic rings and/or bear furthersubstituents (see e.g. WO 01 70395, WO 97 10248 and WO 99 41290), or (b)cyclic σ-, η¹- to η⁴- or η⁶-, mono-, bi- or multidentate ligandscomposed of unsubstituted or substituted mono-, bi- or multicyclic ringsystems, e.g. aromatic or non-aromatic or partially saturated ringsystems, containing carbon ring atoms and optionally one or moreheteroatoms selected from Groups 15 and 16 of the Periodic Table (IUPAC)(see e.g. WO 99 10353). Bi- or multidentate ring systems include alsobridged ring systems wherein each ring is linked via a bridging group,e.g. via an atom from Groups 15 or 16 of the Periodic Table, e.g. N, Oor S, to the transition metal atom (see e.g. WO 02 060963). As examplesof such compounds, i.a. transition metal complexes with nitrogen-based,cyclic or acyclic aliphatic or aromatic ligands, e.g. such as thosedescribed in the applicant's earlier application WO-A-9910353 or in theReview of V. C. Gibson at al., in Angew. Chem. Int. Ed., engl., vol 38,1999, pp 428-447 or with oxygen-based ligands, such as Group 4 metalcomplexes bearing bidentate cyclic or acyclic aliphatic or aromaticalkoxide ligands, e.g. optionally substituted, bridged bisphenylicligands (see i.a. the above review of Gibson et al.). Further specificexamples of non-η⁵ ligands are amides, amide-diphosphane, amidinato,aminopyridinate, benzamidinate, azacycloalkenyl, such astriazabicycloalkenyl, allyl, beta-diketimate and aryloxide. Thedisclosures of the above documents are incorporated herein by reference.It should be noted that the diversity does not affect the applicabilityof the process of the invention, whose essential particle-shapingmeasures remain unaffected by the particular content of the particles tobe shaped.

The preparation of metallocenes and non-metallocenes, and the organicligands thereof, usable in the invention is well documented in the priorart, and reference is made e.g. to the above cited documents. Some ofsaid compounds are also commercially available. Thus, said transitionmetal compounds can be prepared according to or analogously to themethods described in the literature, e.g. by first preparing the organicligand moiety and then metallating said organic ligand (η-ligand) with atransition metal. Alternatively, a metal ion of an existing metallocenecan be exchanged for another metal ion through transmetallation.

A further suitable subgroup of transition metal compounds include thewell known Ziegler-Natta catalysts comprising a transition metalcompound of Group 4 to 6 of the Periodic Table (IUPAC) and a compound ofGroup 1 to 3 of the Periodic Table (IUPAC), and additionally otheradditives, such as a donor. The catalyst prepared by the invention maypreferably form a Ziegler-Natta catalyst component comprising a titaniumcompound, a magnesium compound and optionally an internal donorcompound. Said Ziegler-Natta component can be used as such or,preferably, together with a cocatalyst and/or an external donor.Alternatively, a cocatalyst and/or an external donor may be incorporatedto said Ziegler-Natta component when preparing the catalyst according tothe method of the invention. The compounds, compositions and thepreparation methods are well documented in the prior art literature,i.a. textbooks and patent literature, for the compounds and systems e.g.EP-A-688 794 and the Finnish patent documents nos. 86866, 96615, 88047and 88048 can be mentioned, the contents of each above document areincorporated herein by reference.

The transition metal compounds include also a group of catalyst systemscontaining chromium or nickel.

If several different transition metal compounds are used (mixed dual ormulticatalyst systems), these can be any combinations of the abovetransition metal compounds or of the above transition metal compoundswith other catalyst compounds (including Ziegler-Natta and chromiumoxide systems), e.g. a combination at least of two or more ametallocenes, of a metallocene and a non-metallocene, as well as of ametallocene and/or a non-metallocene with a Ziegler-Natta catalystsystem (which comprises a transition metal compound and a compound of ametal from Group 2 of the Periodic Table, such as a Mg compound).

In all cases it is necessary to ensure that the total quantity ofdissolved catalytic material introduced in to the process will, whenimpregnated on the carrier particles, provide an active transition metalconcentration in the support of 0.001 to 10%, e.g. 0.01 to 4%,preferably 0.01 to 1%, such as 0.05 to 0.8 or 0.1 to 0.5% by weight ofthe dry catalyst system in case of metallocenes and non-metallocenes asdefined above. In case of a Ziegler-Natta catalyst an active transitionmetal concentration in the support can be in the range of 0.01 to 10%,e.g. 0.1 to 4%, especially 0.5 to 3.0%, such as 1.0 to 3.0% or 1.0 to2.0% by weight of the dry catalyst system.

As stated above the catalyst prepared according to the present inventionmay further comprise one or more cocatalysts well known in the art,preferably an activator containing aluminium or boron. Examples of suchactivators are organo aluminium compounds, such as trialkylaluminiumcompound and/or aluminoxane compound, or non-coordination ioniccocatalysts, such as boron activators.

Preferred as cocatalysts for metallocenes and non-metallocenes asdefined above, if desired, are the aluminoxanes, in particular theC₁-C₁₀-alkylaluminoxanes, most particularly methylaluminoxane (MAO).Such aluminoxanes can be used as the sole cocatalyst or together withother cocatalyst(s). Thus besides or in addition to aluminoxanes, othercation complex forming catalysts activators can be used. In this regardmention may be made particularly to boron compounds known in the art.Said activators are commercially available or can be prepared accordingto the prior art literature.

Further aluminoxane cocatalysts are described i.a. in WO 94/28034 whichis incorporated herein by reference. These are linear or cyclicoligomers of having up to 40, preferably 3 to 20, —(Al(R′″)O)— repeatunits (wherein R′″ is hydrogen, C1-C10-alkyl (preferably methyl) orC6-C18-aryl or mixtures thereof).

The use and amounts of such activators are within the skills of anexpert in the field. As an example, with the boron activators, 5:1 to1:5, preferably 2:1 to 1:2, such as 1:1, ratio of the transition metalto boron activator may be used. In case of aluminoxanes, such asmethylaluminumoxane (MAO), the amount of Al, provided by aluminoxane,can be chosen to provide an Al:transition metal molar ratio e.g. in therange of 1:1 to 10 000:1, suitably 5:1 to 8000:1, preferably 10:1 to7000:1, e.g. 100:1 to 4000:1, such as 100:1 to 1500:1.

The quantity of cocatalyst to be employed in the catalyst of theinvention is thus variable, and depends on the conditions and theparticular transition metal compound chosen in a manner well known to aperson skilled in the art.

Any additional components to be contained in the solution comprising thetransition metal compound may be added to said solution before or,alternatively, after the mixing/dispersing step and/or impregnationstep.

Solidification Step

As stated above, particularly, before the recovery of the impregnationmethod of the invention, said solution impregnated in said supportparticles may be subjected to solidification.

This may be effected by polymerisation of a monomer, preferably anolefinic monomer, present in the solution in the pores of theimpregnated support, this according to one embodiment being an alkaneemployed as solvent to form said solution.

In a further embodiment of the invention prepolymerisation is effectedby adding a monomer, in liquid or, preferably, in gaseous state to theimpregnated support suspension in said continuous solvent immisciblewith the impregnated solution. A catalytically active transition metalcomponent or any other catalytically active compound, such as aperoxide, present in the solution within said pores of the supportcauses the monomers to polymerise in said solution. The formed polymermatrix in turn causes the content of the pores to solidify. It is alsopossible to use a combination of the liquid and gaseous monomer(s) whichmay contain the same or different monomer.

Naturally the degree of the prepolymerisation can vary substantially.The amount of monomer used may correspond e.g. to 1 to 500%, preferably1 to 300%, such as 5 to 200%, e.g. 10 to 100% or 30 to 80% wt of theinitial catalyst.

The monomer used for prepolymerising the droplets of the at least twophase system can be any conventional gaseous or liquid monomer. When thesolvent used to form the solution of the catalyst component(s) is notthe solidifying monomer, a gaseous monomer is preferably used. Asexamples, olefin monomers each having 2 to 20 carbon atoms can be used.The olefin can be linear or branched, cyclic or acyclic, aromatic oraliphatic, including ethylene, propylene, 1-butene, 1-pentene,2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene,2,3-dimethyl-1-butene, 1-octene, styrene, vinylcyclohexane etc.

The monomer used for the prepolymerisation can be the same or different,preferably the same, to that used for the actual polymerisation step;also a comonomer can be used in the prepolymerisation step. Theprepolymerisation conditions (temperature, time period etc.) can bechosen analogously to those described in the art. The principles ofprepolymerisation as described e.g. in EP 279 863, the contents of whichare incorporated herein by a reference, can be used. In case a liquidmonomer is used as solution for the catalyst components, the actualprepolymerisation reaction/immobilisation step can be initiated and/orcontrolled e.g. by the temperature. Furthermore, in general, e.g. agaseous monomer feed may be diluted with nitrogen or other inert gas.Also a hydrogen can be used in a known manner during theprepolymerisation to control molecular weight of the prepolymer.

In another preferred embodiment, the solidification of the catalystcomponent(s) in the pores of the support is effected by subjecting theliquid/liquid two phase system containing the support material to anexternal stimulus, such as to a temperature change.

Accordingly, (i) the catalyst solution may be impregnated to the poresof the support material before or after dispersing the support to saidimmiscible solvent, and after the impregnation step, if needed, theimpregnated support may be separated from any residual catalystsolution; and (ii) the dispersed support is subjected to a temperaturechange to cause the solidfication of the catalyst component(s) withinthe pores.

Preferably, in the dispersed/suspended system, the catalyst solutionused is present in the pores of the support. The temperature change ispreferably effected after the impregnated support is suspended in to theimmiscible solvent.

Thus the suspension system may be subjected to a rapid temperaturechange (e.g. within milliseconds and up to 10 seconds) to cause a fastsolidification in the dispersed system or, alternatively, the system canbe heated gradually (e.g. up to 24 h, preferably up to 1 h, suitablywithin 10-30 minutes) to cause a gradual temperature change. E.g. achange of 10 to 100° C., e.g. 30 to 80° C., may be used. The appropriatetemperature change, i.e. an increase or a decrease in the temperature ofan emulsion system, required for the desired solidification rate of thecomponents cannot be limited to any specific range, but naturallydepends on the emulsion system, i.a. on the used compounds and theconcentrations/ratios thereof as well as the used solvents, and ischosen accordingly. It is also evident that any techniques may be usedto provide sufficient heating or cooling effect to the dispersed systemto cause the desired solidification.

Alternatively, the solidification may be effected during the suspendingstep, e.g. by dispersing the impregnated support to a heated (or cooled)solvent as continuous phase.

Furthermore the immobilising of the impregnated catalyst components maybe effected by cross-linking a catalyst component, e.g. an activator,present in said solution with a cross-linking agent. E.g. thecross-linking of an aluminoxane, such as MAO, can be effected in a knownmanner using the principles described e.g. EP-A-685 494, the contents ofwhich are incorporated herein by reference.

Solidification may also be effected by inducing a chemical reactionbetween one or more catalyst compounds in the impregnated solution. Thiscan particularly be the case with catalysts containing Ziegler-Nattacatalyst components, whereby e.g. the compounds of Group 2 and/or 4 ofthe periodic Table (IUPAC) may be caused to react with a precipitatingagent, e.g. a halogenating and/or reducing agent, to form a catalystcomponent which solidifies in the pores of the carrier. An externalstimulus, suitably a temperature change of the system, can also be usedin case of a solidifcation by chemical reaction for inducing and/oraccelerating the chemical reaction between the compounds present in thepores of the support, especially in case of Ziegler-Natta catalystcomponents. The methods and agents causing the solidification are withinthe skills of an expert in the field of Ziegler-Natta chemistry.

The “one phase” change as usable for the formation of a at least twophase system can also be utilised for solidifying the catalyticallyactive contents within the pores of the support by, again, effecting atemperature change in the dispersed system, whereby the solvent used inthe solvent of the catalyst solution present in the pores becomesmiscible with the fluorous continuous phase so that the pores becomeimpoverished of the solvent and the solidifying components remaining inthe pores start to solidify. Thus the immisciblity can be adjusted withrespect to the solvents and conditions (temperature) to control thesolidification step.

The miscibility of fluorous solvents with organic solvents is known fora skilled person and can be chosen accordingly. Also the criticaltemperatures needed for the phase change are available from theliterature or can be determined using methods known in the art, e.g. theHildebrand-Scatchard-Theorie. Reference is also made to the articles ofA. Enders and G. and of Pierandrea Lo Nostro cited above.

The solid catalyst particles recovered can be used, after an optionalwashing step, in a polymerisation process of an olefin. Alternatively,the separated and optionally washed solid particles can be dried toremove any solvent present in the particles before use in thepolymerisation step. The separation and optional washing steps can beeffected in a known manner, e.g. by filtration and subsequent washing ofthe solids with a suitable solvent.

Accordingly the formed particles may have an average size range of 1 to500 μm, e.g. 5 to 500 μm, advantageously 5 to 200 μm, such as 10 to 100μm, or even 5 to 50 μm all sizes of which may be usable, depending onthe polymerisation the catalyst is used for, and are advantageouslyessentially spherical in shape.

Thus, the particle size of the catalyst particles of the invention isdetermined by the size of the suspended carrier particles. The initialcarrier particle size may be increased, if desired, by thesolidification procedure.

Polymerisation Process

The catalyst system of the invention can then be used alone or togetherwith an additional cocatalyst(s) in the actual polymerisation step in amanner known in the art.

The olefin to be polymerised using the catalyst system of the inventioncan be any olefin polymerisable in a coordination polymerisationincluding an alpha-olefin alone or as a mixture with one or morecomonomers. Preferable olefins are ethylene or propene, or a mixture ofethylene or propene with one or more alpha-olefin(s). Preferablecomonomers are C2-C12-olefins, preferably C4-C10-olefins, such as1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,1-octene, 1-nonene, 1-decene, as well as diene, such as butadiene,1,7-octadiene and 1,4-hexadiene, or cyclic olefins, such as norbornene,and any mixtures thereof.

Polyethene and any copolymers thereof are particularly contemplated, asare polypropylene homopolymers and any copolymers thereof.

Furthermore, the catalyst system of the invention can be used for thepolymerisation of long chain branched alpha-olefins (with 4 to 40 Catoms), alone or together with short chain branched alpha-olefins.

Polymerisation may be effected in one or more, eg one, two or threepolymerisation reactors, using conventional polymerisation techniques,in particular gas phase, solution phase, slurry or bulk polymerisation.Polymerisation can be a batch or continuous polymerisation process.Generally a combination of slurry (or bulk) and at least one gas phasereactor is preferred, particularly with gas phase operation coming last.

For slurry reactors, the reaction temperature will generally be in therange of 60 to 110° C. (e.g. 85-110° C.), the reactor pressure willgenerally be in the range 5 to 80 bar (e.g. 50-60 bar), and theresidence time will generally be in the range 0.3 to 5 hours (e.g. 0.5to 2 hours). The diluent used will generally be an aliphatic hydrocarbonhaving a boiling point in the range −70 to +100° C. In such reactors,polymerisation may, if desired, be effected under supercriticalconditions.

For gas phase reactors, the reaction temperature used will generally bein the range 60 to 115° C. (e.g. 70 to 110° C.), the reactor pressurewill generally be in the range 10 to 25 bar, and the residence time willgenerally be 1 to 8 hours. The gas used will commonly be a non-reactivegas such as nitrogen or propane together with monomer (e.g. ethylene orpropylene).

Generally the quantity of catalyst used will depend upon the nature ofthe catalyst, the reactor types and conditions and the propertiesdesired for the polymer product. Conventional catalyst quantities, suchas described in the publications referred herein, may be used.

With the method of the invention a catalyst system with a high bulkdensity and a good morphology is obtained and the catalyst exhibits highcatalytic activity. The bulk density and morphology correlate withproduct bulk density and morphology—the so-called “replica effect”. Thusthe catalyst leads to a polymer with an advantageous high bulk density.

EXAMPLES

The following examples are provided by way of illustration of theinvention. All the starting material is commercially available or can beprepared according to or analogously to the methods described in theliterature.

Example 1

Preparation of Complex/MAO-Solution in a Septa Bottle (in Glove Box):

Bis(n-butylcyclopentadienyl) zirconium dichloride complex (Eurocen 5031,available from Witco) was dissolved in MAO-toluene solution (30%-wt.MAO, supplied by Albemarle) at room temperature and the mixture obtainedwas stirred for one hour.

The amount of complex corresponds to the desired Al/Zr ratio, theZr-loading can be adjusted by varying the amount of the complex and/orMAO-solution in toluene.

Amounts of Catalyst Components in Examples 1 to 4: Example Al/ w_(Zr)[% - m_(complex) V_(MA0,30%) no. Zr wt.] [mg] [ml] Ex. 1 200 0.220 47.35.17 Ex. 2 300 0.315 24 4 Ex. 3 445 0.093 16.4 4 Ex. 4 1200 0.035 6 4Catalyst Preparation:

In a 200 ml glass reactor 3 ml of a complex/MAO-solution in toluene (asprepared according to one of the above examples 1 to 4) was added to awell-stirred (200 rpm) suspension of 2 g of silica carrier (SP9-391 fromGrace, calcinated for 10 h at 600° C., added in glove box to thereactor) in 40 ml octadecafluorooctane (=perfluorooctane, available fromAldrich, stripped for 10 minutes with nitrogen, or 98% from P&M Invest,Moscow, Russia) at room temperature. The amount of the solution of thecatalyst components corresponded to the pore volume of the silica.Stirring of the two phase mixture was continued for 10 minutes afterwhich the complex/MAO solution had been completely sorbed by the silica,resulting in a suspension of the impregnated silica in theoctadecafluorooctane.

To this suspension was then added, at room temperature, 500 mbars ofethylene. When the added ethylene was consumed (pressure decrease) moreethylene was added. Total amount of ethylene corresponded to the desireddegree of prepolymerisation. Per g of polyethylene, about 3.5 barsethylene was added in total.

To the prepolymerised particles was then added 20 ml of pentane, themixture was stirred for one minute and then all liquid(octadecafluorooctane+pentane) was removed. The catalyst was dried for 1h at 50° C.

Prepolymerisation Results: Example no. m_(Silica) [g] yield [g] Ex. 12.0 3.89 Ex. 2 2.2 3.85 Ex. 3 2.15 3.82 Ex. 4 2.04 3.65Test Polymerisations:

The obtained catalyst of examples 1 to 4 were subjected to aconventional slurry polymerisation of ethylene in isobutane, 2-1polymerization reactor Conditions: Temperature: 80° C. Slurry media:1200 ml isobutane (Messer Griesheim 2.5) Comonomer:  30 ml of 1-hexene(Borealis polymerisation grade), batch wise fed Monomer: 5 bars partialpressure of ethylene (Borealis polymerisation grade) Catalyst amount: 200 mg

Polymerization Results: bulk run Example Activity density time no.[kg_(PE)/(h · g_(Zr))] [kg/m³] [h] Remarks Ex. 1 955 388 1 Ex. 2 1130403 1 Ex. 3 2070 410 1 Ex. 3 2660 470 3 3 hours run Ex. 4 3653 1

As can be seen from the results the catalysts prepared according to theinvention produce a polymer product with high bulk densities.

1. A process for producing a supported olefin polymerisationpolymerization catalyst comprising a compound of a transition metal ofGroup 3 to 10 of the Periodic Table (IUPAC), comprising suspending aporous particulate support material in a liquid/liquid at least twophase system which comprises a solution of one or more catalystcomponents and a solvent immiscible therewith, to impregnate saidsolution into the pores said support material, wherein the activetransition metal concentration in the support is from 0.001 to 10% byweight of the dry catalyst system.
 2. The process according to claim 1,further comprising immobilizing said catalyst component(s) of saidsolution present in the pores of said dispersed support particles.
 3. Aprocess for producing a supported olefin polymerization catalyst,wherein said supported olefin polymerization catalyst comprises compoundof a transition metal of Group 3 to 10 of the Periodic Table (IUPAC),comprising suspending porous support particles, wherein the porescontain a solution of one or more catalyst components, in a solventimmiscible with said solution forming a liquid/liquid at least two phasesystem, and solidifying said solution phase within the pores of thedispersed support.
 4. The process according to claim 1, wherein asolvent is used to form said solution.
 5. The process according to claim4, wherein said solvent is an organic solvent or a mixture thereof. 6.The process according to claim 5 wherein said solvent is selected from alinear, branched, or cyclic alkane or alkene, an aromatic hydrocarbonand/or a halogen-containing hydrocarbon or a mixture thereof.
 7. Theprocess according to claim 1, wherein said immiscible solvent whichforms the continuous phase is an inert solvent or a mixture thereof. 8.The process according to claim 1, wherein said immiscible solvent whichforms the continuous phase comprises a fluorinated hydrocarbon, afunctionalized derivative thereof, or a mixture thereof.
 9. The processaccording to claim 1, wherein said immiscible solvent which forms thecontinuous phase comprises a perfluorinated hydrocarbon, afunctionalized derivative thereof, or a mixture thereof.
 10. The processaccording to claim 9, wherein said immiscible solvent comprises a semi-,highly, or perfluorinated hydrocarbon, a functionalized derivativethereof, or a mixture thereof.
 11. The process according to claim 9,wherein said immiscible solvent comprises a perfluorohydrocarbon, afunctionalized derivative thereof, or a mixture thereof.
 12. The processaccording to claim 9, wherein said immiscible solvent comprises asemifluorohydrocarbon, a functionalized derivative thereof, or a mixturethereof.
 13. The process according to claim 1, wherein said particlesare suspended in said immiscible solvent before or after mixing of saidsolution therewith.
 14. The process according to claim 1, wherein saidparticles are suspended in said solution before mixing of said solutionto with said immiscible solvent.
 15. The process according to claim 1,wherein the mixture is made to a one phase liquid by adjusting thetemperature, the support particles are added to the mixtures and thetemperature is changed to break the one phase to a two phase system. 16.The process according to claim 1, wherein the volume of said solutiondoes not exceed the total pore volume of the carrier particles in saidsuspension.
 17. The process according to claim 1, wherein the solutionimpregnated in said support particles is subjected to solidification.18. The process according to claim 17, wherein the solidification of thecatalyst component(s) in the pores of the support is effected bysubjecting the two phase system containing the support material to atemperature change.
 19. The process according to claim 18, wherein saidtemperature change treatment comprises subjecting the two phase systemcontaining the support material to a gradual temperature change of up to10° C. per minute.
 20. The process according to claim 18, wherein saidtemperature change treatment comprises subjecting the two phase systemcontaining the support material to a temperature change of more than 40°C. within less than 10 seconds.
 21. The process according to claim 18,wherein (i) the catalyst solution is impregnated into the pores of thesupport material before or after dispersing the support to saidimmiscible solvent; and (ii) the dispersed support is subjected to atemperature change to cause the solidification of the catalystcomponent(s) within the pores.
 22. The process according to claim 17,wherein said solidification is effected by polymerization of an olefinicmonomer present in said solution.
 23. The process according to claim 22,wherein the olefinic monomer is the solvent used to form said solution.24. The process according to claim 22, wherein a gaseous olefinicmonomer is added to the liquid/liquid two phase system to effect theprepolymerization of said monomer in said impregnated solutioncontaining the catalyst particle(s).
 25. The process according to claim17, wherein the solidification is effected by cross-linking an activatorwith a cross-linking agent.
 26. The process according to claim 17,wherein the solidification is effected by inducing within said particlesa chemical reaction which yields a solid product containing saidcatalyst.
 27. The process according to claim 1, wherein the transitionmetal compound is of Group 4 to 6 of the Periodic Table (IJPAC).
 28. Theprocess according to claim 1, wherein the transition metal compound is acompound of formula (I):(L)_(m)R_(n)MX_(q)  (I) wherein M is a transition metal as defined inclaim 1 or claim 27 and each X is independently a σ-ligand, each L isindependently an organic ligand which coordinates to M, R is a bridginggroup linking two ligands L; m is 1, 2 or 3; n is 0 or 1; q is 1, 2 or3; and m+q is equal to the valency of the metal.
 29. The processaccording to claim 27, wherein the transition metal compound is ametallocene.
 30. The process according to claim 27, wherein thetransition metal compound is a non-metallocene.
 31. The processaccording to claim 27, wherein the transition metal compound forms aZiegler-Natta catalyst system.
 32. The process according to claim 1,wherein said catalyst further comprises an activator/cocatalystcontaining aluminum or boron as said catalyst component.
 33. The processaccording to claim 1, wherein the solid catalyst particles are recoveredfrom said immiscible solvent and subjected to washing and drying. 34.The process for (co)polymerising an olefin in the presence of a catalystproduced according to claim 1 or claim
 3. 35. A catalyst which isobtainable according to the process of claim 1 or claim
 3. 36. The useof a catalyst produced according to claim 1 or claim 3 for the homo- orcopolymerisation of olefins.
 37. A polyolefin which is obtainable usinga catalyst of produced according to claim 1 or claim
 3. 38. The processaccording to claim 1 or claim 3, further comprising solidifying saidimpregnated solution present in the pores of said support particles. 39.The process according to claim 2, further comprising recovering thesolid catalyst particles from said immiscible solvent.
 40. The processaccording to claim 3, wherein the active transition metal concentrationin the support is from 0.001 to 10% by weight of the dry catalystsystem.
 41. The process according to claim 1, wherein said immisciblesolvent comprises a C3-C30 perfluoroalkane, -alkene, or -cycloalkane.42. The process according to claim 41, wherein said immiscible solventcomprises a C4-C10 perfluoroalkane, -alkene, or -cycloalkane.
 43. Theprocess according to claim 42, wherein said immiscible solvent comprisesa perfluorohexane, perfluoroheptane, perfluorooctane, or perfluoro(methylcyclohexane), or a mixture thereof.
 44. The process according toclaim 12, wherein said immiscible solvent comprises a semifluorinatedn-alkane, a perfluoroalkyl-alkane, or a mixture thereof.
 45. The processaccording to claim 19, wherein said temperature change treatmentcomprises subjecting the two phase system containing the supportmaterial to a gradual temperature change of up to 0.5 to 6° C. perminute.
 46. The process according to claim 45, wherein said temperaturechange treatment comprises subjecting the two phase system containingthe support material to a gradual temperature change of up to 1 to 5° C.per minute.
 47. The process according to claim 19, wherein saidtemperature change treatment comprises subjecting the two phase systemcontaining the support material to a temperature change of more than 50°C. within less than 6 seconds.
 48. The process according to claim 21,wherein after step (i) and before step (ii) the impregnated support isseparated from any residual catalyst solution.
 49. The use of a catalystproduced according to claim 1 or claim 3 for the homo- orcopolymerization of C₂ to C₁₀ α-olefines.
 50. The use of a catalystproduced according to claim 1 or claim 3 for the homo- orcopolymerization of C₂ to C₁₀ propene or ethene olefines, or copolymersthereof.